Hydrofining catalyst and process using same



July 16, 1968 R. J. BERTOLACINI ETAL 3,393,148

HYDROFINING CATALYST AND PROCESS USING SAME Filed Nov. 30, 1965 2 wmhm2O mmao:

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United States Patent 3,393,148 HYDROFINING CATALYST AND PROCESS USINGSAME Ralph J. Bertolacini, Chesterton, Ind., and Erwin R. Strong, Jr.,Flossmoor, Ill., assignors to Standard Oil Company, Chicago, 111., acorporation of Indiana Filed Nov. 30, 1965, Ser. No. 510,656 19 Claims.(Cl. 208-264) This invention relates to the hydroprocessing of heavy gasoils and hydrocarbon residua. More particularly, it relates to a novelcatalyst for the hydroprocessing of heavy gas oils and hydrocarbonresidua and a process employing same.

Petroleum crudes are composed of a large variety of hydrocarbons, whichinclude heavy distillates and hydrocarbon residua. Heavy dist-illatesboil at temperatures above about 570 F. and include the heavy gas oilsand light lubricating oils. The hydrocarbon residua, which are made upof saturates, monoaromatics, polyaromatics, resins and asphalt, arefound to have molecular weights ranging from about 600 to about 1200 orabove. At this time, the complete composition of petroleum is not known.There are many areas in the makeup of the crude where the molecularcompositions of the compounds remain unknown. This is particularly truein the case of the heavy and residual fractions.

Today there are various processes employing numerous refining techniqueswhich are used by petroleum refiners to upgrade the petroleum fractionsobtained from the crudes. These processes, such as isomerization,reforming, hydrocracking, and alkylation are well-known in the art andmay be used successfully to convert various hydrocarbon fractions intouseful products. However, such processes do not convert effectively thehigher-boiling feed stocks and fractions into sufficient quantities ofuseable products, such as motor fuels and heating fuels. Among thesehigher-boiling hydrocarbons are the heavy gas oils and the hydrocarbonresidua. Such fractions have not been exploited fully by the refiner.Attempts to refine these heavy materials have shown, for the most part,that the processing must be done at such high severities that suchprocessing is unattractive. These refractory materials give relativelylow yields of usable products. The normal refining processes will notconvert them into economical quantities of products. In general, thetypical hydrocracking process will not convert efficiently suchrefractory heavy hydrocarbons to useable products. Accordingly, aprimary object of the present invention is to provide a catalyst thatcan be used effectively to convert the refractory, higher-boiling gasoils and residual hydrocarbons to more useable products and a processusing such a catalyst.

Hydrocarbon residua are, for the most part, byproducts of processeswhich are primarily used to obtain other petroleum products. Theresidual fuel oils are examples of such hydrocarbon residua. Commercialresidual fuel oils have gravities which may vary between 8.9 and 235API, flash points within the range of about 150 to about 450 F., andpour points within a range of about -55 to about 50 F. Their Conradsoncarbon residues may fall within a range of about 0.1 to about 11.5% andtheir boiling points may fall within a range of about 300 to about 1100F. Such residual fuel oils have been used generally to supply heat.

The heavier fractions of the various petroleum crudes will containappreciable amounts of sulfur and nitrogen, as well as certain so-calledheavy metals. For example, a vacuum reduced crude may be found tocontain as much as 100 parts per million nickel. Metals such as thesedeleteriously affect the life of any catalyst over which thehydrocarbons containing such metals are being processed.

3,393,148 Patented July 16, 1968 "ice In upgrading the heavier fractionsof a petroleum crude, it is ultimately required that a portion of thenitrogen be removed from the heavy-gas-oil fraction and that asubstantial amount of the heavy metals be removed from the fractionboiling above 650 F., this latter material being sent usually to acatalytic cracker for an additional treatment.

Hydroprocessing may be used in the upgrading of heavier petroleumfractions to usable petroleum products. It comprises the contacing ofthe hydrocarbon material that is being processed with a suitablecatalyst under suitable conditions in the presence of hydrogen. Theoutstanding growth of catalytic reforming and the large amounts ofhydrogen resulting therefrom have advanced the economic attractivenes ofhydroprocessing. In such a process, not only are a great deal of thesulfur and a large percentage of the nitrogen removed from thehydrocarbon material being processed, but also the hydrocarbon materialis hydrocracked to yield some usable hydrocarbon products.

Hydrocracking is a general term which is applied to petroleum refiningprocess employing destructive hydrogenation wherein hydrocarbon feedstocks which have relatively high molecular weights are converted tolowermolecular-weight hydrocarbons at elevated temperature and pressurein the presence of a suitable catalyst and a hydrogen-containing gas.Hydrogen is consumed in the conversion of organic nitrogen to ammoniaand sulfur to hydrogen sulfide, in the splitting of high-molecularweightcompounds into lower-molecular-weight compounds, and in the saturationof olefins and other unsaturated compounds.

Suitable catalysts have been developed for the hydroprocessing ofhydrocarbon fractions boiling at temperature within the light-gas-oilboiling range. In this hydroprocessing treatment, the feed stock isdestructively hydrogenated to lower-molecular-weight material.Typically, such catalysts comprise cobalt, molybdenum, and their oxidesand sulfides on a solid inorganic-oxide support such as alumina.However, these catalysts will not convert in an efiicient manner suchrefractory hydrocarbon materials as the heavy gas oils and hydrocarbonresidua. We have found a catalyst which will convert the heavy gas oilsand hydrocarbon residua into more usable materials and a hydroprocessingprocess that uses such a catalyst.

Briefly, we have prepared a catalyst which is surprisingly useful forhydroprocessing heavy gas oils and hydrocarbon residua. This catalyst isa solid catalytic composition which comprises at least one hydrogenationcomponent on a solid inorganic-oxide support comprising alarge-pore-diameter alumina having a surface area within the range ofabout 150 to about 500 square meters per gram and an average porediameter within the range of about to about 200 angstroms. Suitably,this catalyst comprises a hydrogenation metal of Group VI-A of thePeriodic Table and a hydrogenation metal of Group VIII of the PeriodicTable on a large-pore-diameter alumina having a surface area within therange of about to about 500 square meters per gram and an average porediameter within the range of about 100 to about 200 angstroms. ThePeriodic Table to which We have referred is published on page 2 ofModern Aspects of Inorganic Chemistry, H. J. Emeleus and I. S. Anderson,D. Van Nostrand Company, Inc., New York, N.Y., 1949.

We have also prepared a solid catalytic composition wherein the supportis further characterized in that a zeolitic molecular sieve is suspendedin the matrix of the alumina and have found that this is an effectivecatalyst for the hydroprocessing of heavy gas oils and hydrocarbonresidua.

Our catalyst and a process employing such a catalyst can be understoodmore easily through the studying of the following discussion and figure.The figure presents a comparison of the denitrogenation activities offour catalysts, three of which art typical of our invention, obtainedunder hydroprocessing conditions.

We have prepared a catalyst that can be used for the hydroprocessing ofheavy gas oils and hydrocarbon residua. This catalyst typicallycomprises a hydrogenation metal of Group VI-A of the Periodic Table anda hydrogenation metal of Group VIII of the Periodic Table on a solidinorganic-oxide support comprising a large-porediameter alumina having asurface area Within the range of about 150 to about 500 square metersper gram and an average pore diameter within the range of about 100 toabout 200 angstroms. It is desirable that such an alumina be in one ofthe well-known catalytically active forms, such as gamma-alumina.Although such alumina may be pure, it may contain also minor amounts ofother oxides that are inert under the conditions at which it will beused. Such an alumina can contain a small amount of silica for stabilitywithout creating undesirable effects in our process. Desirably, theamount of silica is within the range of about 1 to about weight percent.It is essential that the alumina in our catalyst have large porediameters. The average pore diameter of the alumina should be within therange of about 100 to about 200 angstroms, suitably within the range ofabout 125 to about 180 angstroms, and preferably within the range ofabout 135 to about 160 angstroms; the surface area should be within therange of about 150 to about 500 square meters per gram, suitably withinthe range of about 300 to about 350 square meters per gram, andpreferably within the range of about 320 to 340 square meters per gram.Suitable aluminas can be purchased from manufacturers of reformingcatalysts. For example, Nalco HF-type aluminas having surface areaswithin the range of about 300 to about 350 square meters per gram areavailable from the Nalco Chemical Company. These HF-type aluminas can beobtained with pore volumes varying from as low as 0.54 cubic centimetersper gram to as high as 2.36 cubic centimeters per gram and correspondingaverage pore diameters within the range of about 72 to about 305angstroms. Therefore, those Nalco HF-type aluminas which have thedesired physical properties are suitable as the inorganic-oxide supportof our catalyst.

The alumina desired as a support in our catalyst has a much higheraverage pore diameter than the aluminas used in conventional catalyst.The use of the alumina having a large average pore diameter as a supportin a catalyst for hydroprocessing heavy gas oils and hydrocarbon residuaresults in a catalyst having improved denitrogenation activity, improveddesulfurization activity, and improved hydrocarbon-conversion activity.

We have found that a suitable embodiment of our solid catalyticcomposition comprises a hydrogenation metal of Group VI-A of thePeriodic Table and a hydrogenation metal of Group VIII of the PeriodicTable on an inorganic-oxide support of a large-pore-diameter aluminahaving an average pore diameter within the range of about 100 to about200 angstroms and a surface area within the range of about 150 to about500 square meters per gram. The combined amounts of the hydrogenationmetals are within the range of about 3 to about 35 weight percent basedupon said composition. Typically, the hydrogenation metal of Group VIAis molybdenum and the hydrogenation metal of Group VIII is cobalt. Whenthese two metals are the hydrogenation components, the molybdenum shouldbe present in an amount within the range of about 4.5 to about 26 weightpercent, calculated as molybdenum trioxide and based upon saidcomposition, and the cobalt should be present in an amount Within therange of about 1.3 to about 5.2 weight percent, calculated as cobaltoxide and based upon said composition. A typical embodiment of ourcatalyst comprises 3 weight percent cobalt and 14 weight percentmolybdenum,

both metals being calculated as the oxides, on a largepore-diameteralumina having an average pore diameter within the range of about toabout 200 angstroms and a surface area Within the range of about 1.50 toabout 500 square meters per gram. A preferred embodiment of our catalystcomprises 3 Weight percent cobalt and 14 weight percent molybdenum, bothmetals being calculated as the oxides, on a large-pore-diameter aluminahaving an average pore diameter within the range of about to aboutangstroms, .and a surface area within the range of about 300 to about350 square meters per gram.

We have found further that our catalytic composition is improved if azeolitic molecular sieve is suspended in the matrix of the alumina. Themolecular sieve may be present in an amount within the range of about 1to about 50 weight percent based upon the combined weight of sieve andalumina. Preferably, the molecular sieve is present in an amount withinthe range of about 5 to about 30 weight percent based upon the combinedweight of sieve and alumina.

Zeolitic molecular sieves are composed of porous crystalline metalalumino-silicates. The zeolitic structure excavities, which areinterconnected by numerous smaller pores. These pores have essentially auniform diameter at their narrowest cross section. Generally, thisuniform diameter falls within the range of 4 to 15 angstroms. Basically,the network of cavities is a rigid S-dimensional and ionic network ofsilica and alumina tetrahedra. These tetrahedra are cross-linked by thesharing of oxygen atoms. Cations are included in the crystal structureto balance the electrovalence of the tetrahedra. Examples of suchcations are a metal ion, an ammonium ion and a hydrogen ion. One cationmay be exchanged either entirely or partially by another cation. Thiscation exchange is conveniently accomplished through the use ofion-exchange techniques.

Both crystalline alumino-silicate clays and amorphous alumino-silicatesmay be readily distinguished from the zeolites. Crystallinealumino-silicate clays, e.g., bentonite, have Z-dimensional structures.Amorphous aluminosilicates, e.g., a synthetic silica-alumina crackingcatalyst, have random structures.

In the case of a particular zeolitic molecular sieve, theiutracrystalline pores can be varied in size by replacing at least apart of exchangeable cations with other suitable ions. Such zeolitiesmay be used for drying purposes, for catalytic purposes, and forhydrocarbon-type-separation purposes.

Either natural or synthetic molecular sieves may be used I in ourproposed catalyst. Examples of natural molecular sieves are erionite,mordenite, chabazite, faujasite, gmelinite, and the calcium form ofanalcite. Examples of synthetic zeolitic molecular sieves are Type X,Type Y, Type A, Type D, Type L, Type R, Type S and Type T molecularsieves. Zeolitic molecular sieves can be activated by driving out of thesieves a major portion of the water of hydration. The characteristics ofboth natural and synthetic molecular sieves and the methods forpreparing them have been presented in the chemical art.

The catalyst for hydroprocessing heavy gas oils and hydrocarbon residua,as proposed herein, can be prepared by incorporating the cobalt andmolybdenum metals into the alumina support through the use of an aqueoussolution of a heat-decomposable compound of the particular metal. In thecase of cobalt, a solution of cobalt nitrate, cobalt acetate, cobaltformate, or a solution of such metal compound and a soluble complexingagent, can be used to impregnate the cobalt on the alumina support. Inthe case of molybdenum, an aqueous solution of ammoniumhepta-molybdateor a solution of molybdenum trioxide in ethanolamine may be used toimpregnate the molybdenum on the support. Following these impregnationsthe resulting material is dried and calcined. In the case where amolecular sieve is suspended in the alumina, the catalyst support isprepared by reducing the zeolite to a small particle size, blending thezeolite particles with the alumina hydrogel, and drying the resultngblend. The cobalt and molybdenum may be impregnated then on the supportcomprising the molecular sieve suspended in the alumina by techniquesdiscussed above. The resultant catalyst can be used under suitablehydroprocessing conditions to convert the refractory high-boilinghydrocarbons into lowermolecular-weight compounds, some of which may beused in motor fuels and heating fuels.

Although our catalyst is particularly suitable for the hydroprocessingof heavy gas oils and hydrocarbon residua, it may be used also tohydroprocess light gas oil, light catalytic cycle oils, and the like.

Such a ctalyst as discussed above may be used in a process forhydroprocessing heavy gas oils and hydrocarbon residua. In this process,heavy metals, such as vanadium and nickel need not be removed from thefeed stock. For example, as much as 300 parts per milion vanadium and asmuch as 100 parts per milion nickel can be tolerated. In addition, thenitrogen does not have to be removed from the feed stock prior to ourprocess. The total nitrogen content of more than 6,000 parts per millioncan be tolerated. Our process is carried out at a temperature within therange of about 750 to about 850 F., preferably, within a range of about770 to about 825 F., and at an operating pressure within the range ofabout 1,000 to about 3,000 p.s.i.g., preferably, within the range ofabout 1,200 to about 2,200 p.s.i.g. The hydrocarbon feed is added at aliquid hourly space velocity within the range of about 0.25 to about 5.0volumes of hydrocarbon per hour per volume of catalyst, preferably,within the range of about 0.5 to about 1.5 volumes of hydrocarbon perhour per volume of catalyst. Hydrogen is added to our process at a ratewithin the range of about 3,000 to about 50,000 standard cubic feet ofhydrogen per barrel of hydrocarbon, preferably within the range of 6,000to 20,000 standard cubic feet of hydrogen per barrel of hydrocarbon. Thehydrogen partial pressure is at least 80% of the operating pressure.

Our process can be carried out in conventional equipment which has beendesigned to withstand the operating conditions. No novel pieces ofseparation and recovery equipment are necessary.

Our process can be used to upgrade high-boiling-hydrocarbon fractions.It is particularly useful in converting those hydrocarbon feeds whichare composed mainly of hydrocarbons which boil above 650 F. An exampleof such a hydrocarbon feed stock is a Cyrus Crude which contains 69.8volume percent material boiling at a temperature of at least 650 F. andwhich has a gravity of 8.9" API, a sulfur content of 4.5 weight percentand which contains 230 parts per million vanadium and 70 parts permilion nickel. A similar feed stock was used in the example set forthhereinafter.

The heavy metals in these various higher-boiling hydrocarbon feed stocksexist in compounds. During the hydroprocessing reactions, thesecompounds which contain metals are decomposed and the metals aresubsequently deposited on the catalyst and in the coke. The coke andmetals may be removed by suitable regeneration techniques; or, if theappropriate conditions exist, the spent catalyst advantageously may bediscarded.

Example weight percent molybdenum, calculated as the metals, on

an alumina support of the type prepared in the United States PatentReissue 22,196. Catalyst A was prepared by blending 29.5 grams of cobaltnitrate with 2,770 grams of the required alumina sol in 300 millilitersof water. To

this blend were added 51 grams of ammonium heptamolybdate in 300milliliters of hot water. The addition of this molybdenum-containingsolution gelled the alumina sol. The gel was dried in air at atemperature of about 250 F. for 16 hours. The resulting powder waspelletted into /s x A pellets. These pellets were subsequently calcinedin air at a temperature of about 1000 F. for about 6 hours.

Catalyst B contains 3 weight percent cobalt and 14 weight percentmolybdenum, calculated as the metals, on a support of alumina which hassuspended therein 25 weight percent of an ammonium-exchanged Type-Ymolecular sieve based upon said support. Catalyst B was prepared byblending 41.5 grams of ammonium-exchanged type-Y molecular sieve with2,080 grams of alumina sol of the type prepared in United States PatentReissue 22,196. A cobalt solution containing 29.5 grams of cobaltnitrate was then added to the resulting blend. This was followed by theaddition of a molybdate solution having been previously prepared byadding 49 grams of ammonium hepta molybdate to 500 milliliters of Water.The molybdate solution gelled the sol. The resulting gel was dried inair at a temperature of about 250 F. for 16 hours. The resulting powderwas pelletted with Sterotex and subsequently calcined in air at atemperature of about 1000" F. for 6 hours.

Catalyst C contains 3 weight percent cobalt and 14 weight percentmolybdenum, calculated as the metals, on a support of Nalco HF-typealumina. Catalyst C was prepared by increasing the cobalt content andthe molybdenum content of a catalyst containing 3 weight percentcobalt-oxide and 14 weight percent molybdenum trioxide which had beenobtained from the Nalco Chemical Company. A solution was prepared byadding 18.2 grams of ammonium hepta-rmolybdate and 6.8 grams of cobaltnitrate to about milliliters of water; then 189 grams of the Nalcocatalyst were impregnated with this solution. The impregnated catalystwas then dried in air at a temperature of about 250 F. for about 16hours and subsequently calcined in air at a temperature of 1000 F. for 6hours.

Catalyst D contains 3 weight percent cobalt and 14 weight percentmolybdenum, calculated as the metals, on a support of alumina into thematrix of which ammonium-exchanged type-Y molecular sieves have beensuspended. The molecular-sieve content of the support was 5 weightpercent. This catalyst was prepared by blending 114 grams ofammonium-exchanged type-Y molecular sieves with 1770 grams of NalcoI-lF-type alumina hydrogel (weight is on a dry basis). After sufficientblending, the resulting blend was spray dried at 250 F. Cobalt andmolybdenum were impregnated into the preparation by conventionalcommercial techniques.

Catalyst E contains 3 weight percent cobalt and 14 weight percentmolybdenum, calculated as the metals, on a support of alumina into whichammonium-exchanged type-Y molecular sieves have been suspended. Themolecular-sieve content of the support was 10 weight percent. Thecatalyst was prepared by blending 340 grams of ammonium-exchanged type-Ymolecular sieve with 1544 grams of Nalco HF-type alumina hydrogel(weight is on a dry basis). After sufiicient blending, the resultingblend was spray dried at 250 F. Cobalt and molybdenum were impregnatedinto the preparation by conventional commercial techniques.

Catalyst F contains 3 weight percent cobalt and 14 weight percentmolybdenum, calculated as the metals, on a support of alumina into whichammoniumexchanged type-Y molecular sieves have been suspended.

The support contained 25 weight percent molecular sieves. Catalyst F wasprepared by blending 5 68 grams of ammonium-exchanged type-Y molecularsieves with 1316 grams of Nalco HF-type alumina hydrogel (weight is on adry basis). The resulting blend was then spray dried at a temperature ofabout 250 F. Cobalt and molybdenum were impregnated into the preparationby conventional commercial techniques.

The above catalysts were tested individually in a micro unit todetermine whether they would satisfactorily reduce the nitrogen andsulfur contents of a vacuum residuum. This vacuum residuum was inessence a vacuum reduced crude.. Its physical properties'are summarizedin the following table.

Gravity, API 10.9

ASTM IBP, F 1000+ Ramsbottom carbon, weight percent l7 Sulfur, wt.percent 1.3 Pour point, F. 115 Viscosity:

SSF 275 F. 125 SSF 325 F. 43 Total nitrogen, ppm. 6,300 Metals, p.p. m.l i

Alumina I -1 5.4 Calcium 20 Iron p I 18 Magnesium 6.2 Sodium 75 Nickel41 Vanadium 66 The reactor of the micro unit was A3" in diameter; andwhen it was filled with 40 cc.s of catalyst, the catalystbed depth was8.4 inches. A particular catalyst was charged, to this reactor. It ispresumed that the cobalt and molybdenum in each of these catalyst waspresent in the oxide form, since the catalyst had been calcined in airat 1000 F. prior to the charging. When a particular catalyst had beenput in the reactor, the catalyst was heated to a temperature of about700 F. in nitrogen at," near-atmospheric pressure. Then a hydrogenstream conhydrocarbon was charged to the reactor at a liquid hourlyspace velocity of about 0.6 volume of hydrocarbon per hour per volume ofcatalyst and the hydrogen was added at the rate of approximately 4standard cubic feet of hydrogen per hour (about 20,000 standard cubicfeet of hydrogen per barrel of hydrocarbon). After the cat-' alyst hadbeen on stream for 20 hours, the temperature was raised from 750 to 810F. and then maintained at this latter temperature for the remainder ofthe test. Each test was continued for a period of time of 2 to- 4 days.

ity of that catalyst over the time of the test. Denitrogenationactivity, desulfurization activity, or both, were considered for each ofthese tests. Since previous data have indicated that denitrogenation forthis particular feed stock followers a zero-order-reaction mechanism andthat desulfurization follows a first-order-reaction mechanism, rateconstants could be calculated for denitrogenation and desulfurizationoccurring in a particular test. Either the denitrogenation activity orthe desulfurization activity was calculated as 100 times the ratio ofthe observed rate constant for the particular reaction from a particulartest divided by a standard rate constant.

The results of tests made with Catalyst A, Catalyst B, Catalyst C, andCatalyst F are presented in the figure, which shows the denitrogenationactivity of each of these catalysts over the length of the particulartest run. The denitrogenation activity of Catalyst A, the catalysthaving a support of the prior-art alumina, is inferior to those of theother three catalysts, which include Catalyst C.

.5 Catalysts were evaluated for the maintenance of the activ- Catalyst Chas a Nalco HF-type alumina support. Catalyst C and Catalyst B,containing the prior-art alumina and 25 Weight-percent molecular sievesbased upon the support, have almost similardenitrogenation.activitiesyhowever, Catalyst'F, which contains NalcoHF-type alumina and 25 weight percent molecular sieves based upon'thesupport, has a denitrogenation activity which is far superior to thoseof the other three. catalysts. Q:

In addition to the results shown in the figure, th ese tests furnisheddata, which indicate that the desulfurization activities of these fourcatalysts are essentially equivalent.

The results of tests using Catalysts D, E, and F indicate that changingthe molecular sieve content of the catalyst from the 5 weight percent inCatalyst D to the 25 weight percent in Catalyst F does not appreciablyafiect the denitrogenation activity of the catalyst. These amounts ofmolecular sieves are based upon the support. In each of the Catalysts D,was used.

The results of the above tests indicate that our catalytic compositionhas advantages over those presented in the prior art for hydroprocessingheavy gas oilsand petroleumtresidua. g p

-In a specific, embodiment of our process for hydroprocessinghydrocarbon residua, approximately 71,000

E, and F, Nalco HF-type alumina barrels per stream day (BSD) of anatmospheric reduced crude fraction of a Cyrus Crude are introduced intothe reaction-zone. The raw crude hasasulfur content of 3.6Weight-percent sulfur and a gravity of 17.7 API; the atmospheric reducedcrude fraction, a sulfur content of 4.5 weight percent sulfur and agravity of 93 ARI. Also introduced into thereaction zone are 125 millionstandard cubic feet ofhydrogen vper day and 6,000 standard cubic feet ofrecycle ,gasper barrel of hydrocarbonprocessed. Operating. conditions inthe reaction zone include a temperatureof about 800 F,, a pressure of1500 p.s.i.g., and a liquid hourly space velocity of 0 .7. 4 volumes,,of

hydrocarbon per hour per volume of catalyst. Thecatalyst employed is acatalystpomprising ,3 weight percent cobalt and 14 weight percentmolybdenum, calculatedas the oxides, on a support ofNalcoHF-typealumina. Approximately 104,250 BSD of reconstituted CyrusCrude are obtained. This reconstituted Cyrus Crude has 'a sulfur levelof 1.5 weight percent sulfur and agravity of 28.9 API. Whiletheatmospheric reduced crude charged to-the reaction zone is about 95%material boiling at a temperature of at least 650 F., the product isonly about 67% material boiling at a temperature of at least 650 F.

It is to be understood that the examples and specific embodimentpresented herein are for illustrative purposes only and are not intendedto limit thescope of our invention. Y Y

What is claimed is: p I r 1. A solid catalytic composition for thehydroproce ssing of heavy gas oils and hydrocarbon residue w'hichcomposition comprises a hydrogenation metal of Group VI-A of thePeriodic Table and a hydrogenation metal of Group VIII of the PeriodTable on a solid inorganicoxide support comprising a large-pore-diameteralumina having a surface area Within the range of'ab'out' 150 to about500 square meters per gram and an average pore diameter within the rangeof about to about 200 angstroms.

2. The composition of claim 1 further characterized in that said metalof Group VIA and said metal of Group VIII are present in a total amountwithin the range of about 3 to about 35 weight percent based upon saidcomposition.

3. The composition of claim 1 wherein said metal of Group VIA ismolybdenum.

4. The composition of claim 1 wherein said metal of Group VIII iscobalt.

5. The composition of claim 1 wherein said metal of Group VI-A ismolybdenum and is present in an amount within the range of about 4.5 toabout 26 weight percent, calculated as molybdenum trioxide and basedupon said composition.

6. The composition of claim 1 wherein said metal of Group VIII is cobaltand is present in an amount within the range of about 1.3 to about 5.2weight percent, calculated as cobalt oxide and based upon saidcomposition.

7. The composition of claim 1 wherein said metal of Group VI-A ismolybdenum and is present in an amount within the range of about 4.5 toabout 26 weight percent, calculated as molybdenum trioxide and basedupon said composition, and wherein said metal of Group VIII is cobaltand is present in an amount within the range of about 1.3 to about 5.2Weight percent, calculated as cobalt oxide and based upon saidcomposition.

8. The composition of claim 1 wherein said support is furthercharacterized in that a zeolitic molecular sieve is admixed with saidalumina.

9. The composition of claim 8 wherein said molecular sieve is present inan amount within the range of about 1 to about 50 weight percent basedupon said support.

10. The composition of claim 8 wherein said molecular sieve has beenion-exchanged with a salt selected from the group consisting ofalkali-metal salts and alkalineearth-metal salts.

11. The composition of claim 8 wherein said molecular sieve is presentin the hydrogen form.

12. The composition of claim 8 further characterized in that said metalof Group VI-A is molybdenum and is present in an amount Within the rangeof about 4.5 to about 26 weight percent, calculated as molybdenumtrioxide and based upon said composition, said metal of Group VIII iscobalt and is present in an amount within the range of about 1.3 toabout 5.2 weight percent, calculated as cobalt oxide and based upon saidcomposition, and said molecular sieve is the hydrogen form of a Type-Ymolecular sieve and is present in an amount within the range of about 1to about 30 weight percent based upon said support.

13. The composition of claim 8 further characterized in that said metalof Group VI-A is molybdenum and is present in an amount of 21 weightpercent, calculated as molydenum trioxide and based upon saidcomposition, said metal of Group VIII is cobalt present in an amount of3.8 weight percent, calculated as cobalt oxide and based upon saidcomposition, and said molecular sieve is the hydrogen form of a Type-Ymolecular sieve and is present in an amount within the range of about toabout 25 weight percent based upon said support.

14. A process for the hydroprocessing of a feed stock selected from thegroup consisting of heavy gas oils, hydrocarbon residue, and mixturesthereof, which process comprises contacting said feed stock undersuitable hydroprocessing conditions with a catalyst comprising ametallic hydrogenation component on a solid inorganicoxide supportcomprising a large-pore-diameter alumina having a surface area withinthe range of about 150 to about 500 square meters per gram and anaverage pore diameter within the range of about 100 to about 200angstroms.

15. The process of claim 14 wherein said support is furthercharacterized in that a zeolitic molecular sieve is admixed with saidalumina.

16. The process of claim 14 wherein said catalyst comprises ahydrogenation metal of Group VIA of the Periodic Table and ahydrogenation metal of Group VIII of the Periodic Table on a solidinorganic-oxide support comprising a large-pore-diameter alumina havinga surface area within the range of about 150 to about 500 square metersper gram and an average pore diameter within the range of about 100 toabout 200 angstroms.

17. The process of claim 14 wherein said contacting is carried out at atemperature within the range of about 750 to about 850 R, an operatingpressure within the range of about 1000 to about 3000 p.s.i.g., ahydrogen partial pressure of at least of said operating pressure, aliquid hourly space velocity within the range of about 0.25 to about 5.0volumes of hydrocarbon per hour per volume of catalyst, and a hydrogenaddition rate within the range of about 3,000 to about 50,000 standardcubic feet of hydrogen per barrel of hydrocarbon.

18. The process of claim 14- wherein said contacting is carried out at atemperature within the range of about 770 to about 825 R, an operatingpressure within the range of about 1200 to about 2200 p.s.i.g., ahydrogen partial pressure of at least 80% of said operating pressure, aliquid hourly space velocity within the range of about 0.5 to about 1.5volumes of hydrocarbon per hour per volume of catalyst, and a hydrogenaddition rate within the range of about 6,000 to about 20,000 standardcubic feet of hydrogen per barrel to hydrocarbon.

19. The process of claim 17 wherein said catalyst has been subjectedpreviously to a treatment comprising heating said catalyst to atemperature of about 700 F. in nitrogen, passing over said catalyst agas containing hydrogen and hydrogen sulfide at a pressure of p.s.i.g.for 1 hour, heating said catalyst in said gas to the desired operatingpressure, and placing said catalyst under conditions that will be usedin said process.

References Cited UNITED STATES PATENTS 3,143,491 8/ 1964 Berstrom 208743,242,101 3/1966 Erickson et al. 208-254 3,277,018 10/1966 Plank el al208- 3,322,666 5/ 1967 Beuther et al 208--254' DELBERT E. GANTZ, PrimaryExaminer.

SAMUEL P. JONES, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N0 3 ,393,148 July 16, 1968 Ralph J. Bertolacini et al It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:

Column 1, lines 69 and 70, "as much as 100 parts per million nickel"should read as much as 500 parts per million vanadium and as much as 100parts per million nickel Column 2, line 22, process" should readprocesses Column 3, line 5, ".art" should read are Column 4,

lines 23 and 24, "The zeolitic structure ex-cavities" should read Thezeolitic structure exists as a network of relatively smallaluminosilicate cavities Column 5, line 54, "milion" should read millionColumn 6, line 15, "typ sh l r ad Typ -Y Column 7, line 61, "followersshould read follows Column 10, line 36, "to" should read O n Signed andsealed this 20th day of January 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents

1. A SOLID CATALYTIC COMPOSITION FOR THE HYDROPROCESSING OF HEAVY GASOILS AND HYDROCARBON RESIDUE, WHICH COMPOSITION COMPRISES AHYDROGENATION METAL OF GROUP VI-A OF THE PERIODIC TABLE AND AHYDROGENATION METAL OF GROUP VIII OF THE PERIOD TABLE ON A SOLIDINORGANICOXIDE SUPPORT COMPRISING A LARGE-PORE-DIAMETER ALUMINA HAVING ASURFACE AREA WITHIN THE RANGE OF ABOUT 150 TO ABOUT 500 SQUARE METER PERGRAM AND AN AVERAGE PORE DIAMETER WITHIN THE RANGE OF ABOUT 100 TO ABOUT200 ANGSTROMS.
 14. A PROCESS FOR THE HYDROPROCESSING OF A FEED STOCKSELECTED FROM THE GROUP CONSISTING OF HEAVY GAS OILS, HYDROCARBONRESIDUE, AND MIXTURES THEREOF, WHICH PROCESS COMPRISES CONTACTING SAIDFEED STOCK UNDER SUITABLE HYDROPROCESSING CONDITIONS WITH A CATALYSTCOMPRISING A METALLIC HYDROGENATION COMPONENT ON A SOLID INORGANICOXIDESUPPORT COMPRISING A LARGE-PORE-DIAMETER ALUMINA HAVING A SURFACE AREAWITHIN THE RANGE OF ABOUT 150 TO ABOUT 500 SQUARE METERS PER GRAM AND ANAVERAGE PORE DIAMETER WITHIN THE RANGE OF ABOUT 100 TO ABOUT 200ANGSTROMS.